RU2607106C2 - Kit for production of emulsifiable pesticide solution, composition obtained from said kit (versions), method of producing emulsifiable pesticide solutions and crop treatment method - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. Kit for producing an emulsifiable pesticide solution comprises: (a) a water miscible organic solvent selected from a list of: a glycol ether, a glycerol formal, dimethylsulphoxide, gamma-butyrolactone or mixtures thereof, (b) an alkoxylated alcohol having an alkyl chain length from 4 to 24 carbon atoms with ethylene oxide in average amount of 6 to 80 mol and with propylene oxide in average amount of 2 to 60 mol per mol alcohol; and (c) pesticide active ingredient, where alkoxylated alcohol has formula (I) or (II):

CH₃-(CH₂)_x-CH₂-O-(CH₂-CH₂-O)_y-(CH₂-CH(CH₃)-O)_z-H (I)

CH₃-(CH₂)_x-CH₂-O-(CH₂-CH(CH₃)-O)_z-(CH₂-CH₂-O)_y-H (II),

x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60; provided that aromatic or isoparaffinic solvent is absent.

EFFECT: invention increases stability of emulsion.

20 cl, 4 tbl, 5 ex

Description

Technical field

The invention generally relates to the field of agricultural chemistry and, more specifically, to the manufacture of emulsifiable solutions of pesticides. In particular, the invention relates to a kit and to a composition suitable for the manufacture of a wide range of emulsifiable pesticide concentrates. In addition, the invention relates to emulsifiable concentrates obtained from them, and to the use of emulsions obtained by adding emulsifiable concentrates to water, for processing crops. In a final aspect of the invention, a method for processing crops is provided.

State of the art

Agrochemical compositions are intended for the manufacture of a product that is convenient to use, and to obtain uniform distribution of a small amount of active substance over a vast area for processing crops. When creating a composition, a number of factors must be taken into account: type of application, culture to be processed, regional version of agricultural practice; and the last, but no less important factor is the physicochemical properties of the active substance, including the melting point, solubility and chemical stability.

Liquid formulations are preferred by the farmer to obtain spray solutions for several reasons. They can be measured in a volumetric way, easy to handle, spontaneously form stable emulsions or dispersions and, provided the container design is suitable, are usually convenient for rinsing from the packaging. They are also easy to handle in bulk transport systems and usually do not cause problems during use.

An emulsifiable concentrate consists of an active ingredient dissolved in an organic solvent with a sufficient amount of emulsifier added to create an oil-in-water emulsion after adding water to the emulsifiable concentrate. An emulsion is a mixture in which one liquid is suspended in another liquid. In an agrochemical emulsion, water is often a dispersion phase (carrier), while oil droplets consisting of a solvent with an agrochemical active ingredient are dispersed in it.

In 2007/017501, emulsifiable concentrate compositions were disclosed comprising a pesticidal active ingredient, a multi-component solvent system and a multi-component emulsifying system. All examples contain a mixture of aromatic hydrocarbons.

The solvent for use in the emulsifiable concentrate is selected for its ability to solubilize the selected active ingredient. Aromatic and isoparaffin solvents often satisfy this requirement. However, the use of solvents with low flashpoints is becoming increasingly limited as government regulations tighten their transportation and handling. Therefore, there is a need to avoid the use of flammable solvents to solubilize the active ingredient, especially for pesticidal active ingredients.

In order to produce a concentrated emulsion, the emulsifier should be carefully selected to obtain a composition in which the selected agrochemical active ingredient is optimally distributed. The formation of stable concentrated emulsions requires irreversible fixation in an oil drop and strong steric repulsion between particles. Irreversible flocculation or coalescence of emulsions is prevented by creating an energy barrier that is sufficient to prevent oil droplets from drawing closer together. Steric stabilization can be created using surfactants.

The above requirements result in products being developed for a particular active ingredient. This leads to the need to store a wide range of products in the enterprise. Taking into account that the development of a product for a new composition takes a long period of time, the demand for delivery on time in response to the onset of plant diseases increases. Developers of agrochemicals face, on the one hand, an increase in the cost of raw materials and storage facilities and, on the other hand, an increase in the complexity of agrochemical compositions.

EP 1625791 discloses a liquid insecticidal composition comprising a mixture of dimethyl sulfoxide, gamma-butyrolactone and a surfactant of a propylene oxide / ethylene oxide block copolymer in combination with a chloronicotinyl compound.

US 4502861 discloses a milling composition for application to keratinized materials containing cypermethrin, barbituric acid, diethylene glycol ethyl ether, an amine or amide surfactant, and a propylene glycol and ethylene oxide block copolymer.

WO 2007/017501 discloses an emulsifiable concentrate containing phenylsemicarbazone, a solvent system, one or more emulsifiers and optionally additional additives to the composition for use against insect pests.

None of the above compositions disclosed whether a pair of solvent / surfactant is compatible with other active ingredients, in particular with a large variety of pesticidal active ingredients.

There remains a need in the art for an improved method for the manufacture of agrochemical products and for emulsifiable solutions of pesticides, in particular products with an improved environmental profile, which are convenient to manufacture, store and use, and are of economic interest in the manufacture.

The present invention is directed to solving or improving at least some of the problems mentioned above. In particular, the invention is also aimed at producing emulsifiable solutions of pesticides that can reduce storage costs, while not limiting the developer in providing farmers with a wide range of products based on emulsifiable concentrates. Emulsifiable concentrates are able to provide good stability of the emulsion over a long period both at elevated and at low temperatures. In addition, these agrochemical compositions have a reduced environmental impact and are safe to use.

Summary of the invention

Thus, the present invention provides a solvent / surfactant pair suitable for combination with a wide and diverse range of pesticidal active ingredients to formulate emulsifiable solutions of pesticides.

In a first aspect of the present invention, there is provided a kit for the manufacture of an emulsifiable solution of a pesticide, comprising:

(a) a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone or mixtures thereof,

(b) alkoxylated alcohol with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 2 to 60 mol per mole of alcohol; and

(c) a pesticidal active ingredient.

In addition, the present invention relates to a composition for the manufacture of emulsifiable solutions of pesticides obtained from the kit, comprising: a water miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone or mixtures thereof; and alkoxylated alcohol with ethylene oxide in an amount on average of 6 to 80 mol and with propylene oxide in an amount of on average 2 to 60 mol per mole of alcohol.

The beneficial effect possessed by the kit and composition is expressed in the fact that emulsifiable solutions of pesticides can be obtained on their basis in the absence of an aromatic or isoparaffin solvent. Avoiding these flammable solvents provides improved safety.

In a preferred embodiment of the invention, the solvent is dipropylene glycol methyl ether, diethylene glycol monoethyl ether or dipropylene glycol monoethyl ether.

In a preferred embodiment of the invention, the alcohol alkoxylate has the formula (I) or (II), where x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60. More preferably x is from 2 to 14, y is from 10 to 60 and z is from 2 to 45.

In a preferred embodiment of the invention, the kit or composition further comprises a pesticidal active ingredient selected from the list: abamectin, alpha-cypermethrin, cypermethrin, permethrin, deltamethrin, diflubenzuron, flufenoxuron, etofenprox, malathion, pymethrosine, pyriproxifen, azroxorodilodinodin, xroxorodilodinodin, xyrodorfilodilodin, xyrodistorodilodinodin, xyrodorfilodilodin, xyrodorfinodilodin, , iprodione, mancozeb, metconazole, spiroxamine, 2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ether (2,4-D EHE), chlorprofam (CIPC), celodime, metribuzin, prosulfocarb, pendimethalin, butoxyethyl triclopyr ether, trinexapac-ethyl and mixtures thereof.

In a preferred embodiment of the invention, the selected pesticidal active ingredient is cypermethrin, isomer of cypermethrin, or mixtures thereof; preferably the pesticidal active ingredient is cypermethrin.

The solvent / surfactant pair of the invention makes it possible to combine with a wide and diverse range of pesticidal active ingredients to formulate emulsifiable concentrates.

In a preferred embodiment of the invention, the composition comprises:

25-98% diethylene glycol monoethyl ether,

1-15% alkoxysilane alcohol of the formula (I),

1-60% cypermethrin,

0-10% water and

0-0.3% antifoam.

In another preferred embodiment of the invention, the composition for the manufacture of emulsifiable solutions of pesticides contains 250 g / l of trinexapac-ethyl, 150 g / l of alkoxylated alcohol of the formula (I) or (II) and 550 g / l of glycerolformal.

The emulsifying system of the present invention is a system compatible with a wide range of active ingredients. This is an advantage, since only a limited number of solvents and surfactants miscible with water can be stored at the enterprise without restricting the range of commercial products that can be made from a limited number of raw materials. The term “surfactant” describes a compound that may possess the properties of an emulsifying, dispersing or moisturizing agent.

In another aspect of the invention, a method for the manufacture of emulsifiable solutions of pesticides, comprising the steps of:

- obtaining a solution containing a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone, or a combination thereof; and alkoxylated alcohol with ethylene oxide in an amount on average of 6 to 80 mol and with propylene oxide in an amount of on average 2 to 60 mol per mole of alcohol,

- adding to this solution a pesticidal active ingredient miscible with the selected solvent.

In a preferred embodiment, the method comprises the step of:

- heating the preemulsion containing the pesticidal active ingredient to a temperature of from 20 ° C to 60 ° C.

In a final aspect of the invention, there is provided a method of processing a crop, comprising the steps of:

- receiving a kit containing

(a) a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone or mixtures thereof,

(b) alkoxylated alcohol with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 2 to 60 mol per mole of alcohol; and

(c) a pesticidal active ingredient,

- mixing (a) with (b) and (c), thereby obtaining a solution for the manufacture of emulsifiable solutions of pesticides,

- adding this solution to water, emulsifying thereby the pesticidal active ingredient and obtaining an emulsified pesticidal composition containing the active ingredient with a predetermined dose level,

- applying an emulsified pesticidal composition to a crop affected by a disease that is sensitive to the action of the selected active ingredient and dose level.

In a preferred embodiment of the method of the invention, the active ingredient is cypermethrin or trinexapac-ethyl.

In the method of the invention, an emulsifiable agrochemical is made from a preemulsion containing a combination of a solvent and a surfactant, where this combination is found to be compatible with a large number of agrochemical active ingredients. The method according to an embodiment of the invention thus makes it possible to reduce inventories at an enterprise without compromising on the range of products offered to farmers. Emulsified concentrates can be made on demand.

DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise specified, all terms used in the disclosure of the invention, including technical and scientific terms, have a meaning, as it is generally understood by a specialist in the field of technology to which this invention belongs. For a better understanding of the ideas of the present invention, definitions of terms are included by way of further guidance.

When used in this description of the invention, the following terms have the following meanings.

When using in this description of any definitions in the singular, the plural is also provided, unless the context clearly requires otherwise. As an example, “department” refers to one or more than one department.

“Exemplary” as used herein refers to a measurable quantity, such as a parameter, quantity, time duration and the like, and is intended to encompass changes of +/- 20% or less, preferably +/- 10% or less, more preferably +/- 5% or less, even more preferably +/- 1% or less, and even more preferably +/- 0.1% or less of a particular value, as far as such changes are suitable for implementation in the disclosed invention. However, it should be understood that the quantity to which the determinant “for example” refers is itself also specifically disclosed.

The terms “containing”, “containing” and “containing” and “consists of” when used in this description of the invention are synonymous with the terms “include”, “including”, “include” or “containing”, “containing”, “containing” and are inclusive or unavailable, which are defined by the following terms, for example and do not exclude or impede the presence of additional, not listed components, properties, elements, members, stages, known in the art or disclosed in this op Saniya invention.

The expression ʺ% mass.ʺ (percent by mass), here and throughout the description, unless otherwise specified, refers to the relative mass of the corresponding component calculated on the basis of the total mass of the composition.

Enumerating ranges of numerical values by specifying endpoints includes all numbers and fractions included in this range, as well as the listed endpoints.

The term “alkyl” refers to a monovalent straight or branched chain hydrocarbon radical having a specific number of carbon atoms. Alkyl groups may be unsubstituted or substituted with substituents that do not interfere with the specific function of the composition. The carbon chain length can range from 6 to 18 carbon atoms.

The term “alkoxyl” refers to a straight or branched chain monovalent hydrocarbon radical having a specific number of carbon atoms and a carbon-oxygen-carbon bond, may be unsubstituted or substituted with substituents that do not interfere with the specific function of the composition.

The term “non-ionic” refers to a surfactant, that is, a surfactant with one or more uncharged hydrophilic substituents, which generally does not dissociate into ions in solution, unlike anionic and cationic surfactants. Nonionic surfactants are mainly organic compounds having both hydrophilic and hydrophobic groups.

The inventors have discovered a composition that can act as a preemulsion for a large number of agrochemical active ingredients. The composition contains a water miscible organic solvent and a nonionic surfactant.

The organic solvent is selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone, or a combination thereof.

By the term “glycol ether”, as used herein, is meant a compound formed by the reaction of alkylene oxide with alcohols such as methanol, ethanol, propanol, butanol or phenol. Subsequent reaction with additional alkylene oxide leads to the corresponding di-, tri- and higher glycol ethers. The interaction is usually catalyzed by a base.

Glycol ethers can be represented by the structural formula [CH3-CH2 (OH) -CH2-O] n-R, where n is 1, 2 or 3; and R is alkyl, preferably methyl, ethyl, propyl or butyl.

Examples of ethylene glycol ethers are ethylene glycol monomethyl ether (2-methoxyethanol, CH ₃ OCH ₂ CH ₂ OH), ethylene glycol monoethyl ether (2-ethoxyethanol, CH ₃ CH ₂ OCH ₂ CH ₂ OH), ethylene glycol monopropyl ether (2-propoxyethanol, ₃ CH ₂ CH ₂ OCH ₂ CH ₂ OH), ethylene glycol monoisopropyl ether (2-isopropoxyethanol, (CH ₃ ) ₂ CHOCN ₂ CH ₂ OH), ethylene glycol monobutyl ether (2-butoxyethanol, CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OH), ethylene glycol monophenyl ether (2-phenoxyethanol, C ₆ H ₅ OCH ₂ CH ₂ OH), ethylene glycol monobenzyl ether (2-benzyloxy Tanoli, C ₆ H ₅ CH ₂ OCH ₂ CH ₂ OH), diethylene glycol monomethyl ether (2- (2-methoxyethoxy) ethanol, methyl carbitol, CH ₃ OCH ₂ CH ₂ OCH ₂ CH ₂ OH), diethylene glycol monoethyl ether (2- (2-Ethoxyethoxy) ethanol, carbitol cellosolve, CH ₃ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH) and diethylene glycol mono-n-butyl ether (2- (2-butoxyethoxy) ethanol, CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH).

Diethylene glycol monoethyl ether is commercially available under the trademark Carbitol (Carbitol).

Examples of propylene glycol ethers are propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol diphenylene glycol ether , dipropylene glycol methyl ether acetate and tripropylene glycol methyl ether.

In a preferred embodiment of the composition of the invention, the solvent is dipropylene glycol methyl ether or diethylene glycol methyl ether.

Dipropylene glycol methyl ether is commercially available under the trademark Dowanol DPM (Dovanol DPM) from Dow, US. Dipropylene glycol is a hydrophilic glycol ether with a solubility in water of 100% at a temperature of 25 ° C. It has a moderate to slow evaporation rate. For example, Dovanol DPM has a relative evaporation rate of 0.03 (based on an arbitrarily selected evaporation rate of butyl acetate 1.0). It can be represented by the formula CH ₃ O [CH ₂ CH (CH ₃ ) O] ₂ H (one of several isomers).

By the term “glycerol formal”, as used herein, is meant a composition consisting of 5-hydroxy-1,3-dioxane and 4-hydroxymethyl-1,3-dioxolane, usually in a ratio of 60:40. It is obtained from glycerol and formaldehyde. The boiling point of glycerolformal is 191-195 ° C at 760 mm Hg. Art. (0.1 MPa). Glycerol formal is an environmentally friendly alternative to aromatic solvents.

Dimethyl sulfoxide (DMSO) is an organosulfur compound of the formula (CH ₃ ) ₂ SO. This colorless liquid is an important polar aprotic solvent that can dissolve both polar and non-polar compounds. It is miscible with a wide range of organic solvents, as well as with water.

Gamma-butyrolactone, abbreviated GBL, is a hygroscopic colorless oily liquid that is soluble in water.

In another preferred embodiment, the solvent is a 40:60 mixture of dimethyl sulfoxide and gamma-butyrolactone. By the term “40:60 mixture of dimethyl sulfoxide and gamma-butyrolactone”, as used herein, is meant a composition essentially containing dimethyl sulfoxide and gamma-butyrolactone in a ratio of 40% by weight of dimethyl sulfoxide to 60% by weight of gamma-butyrolactone.

These solvents are non-flammable, relatively cheap, easily flowing due to their low viscosity and with improved toxicological profile.

The inventors have found that a composition comprising a water-miscible organic solvent selected from the list is: propylene glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone, or a mixture thereof; and alcohol alkoxylate derived from ethylene / propylene oxide units is particularly preferred for the manufacture of emulsifiable solutions of pesticides. This combination of solvent and non-ionic surfactant has been found to be compatible with a wide range of pesticidal active ingredients.

Preferably, the alkoxylated alcohol has an alkyl chain length of at least 4 carbon atoms, preferably 4 to 24 carbon atoms, more preferably 4 to 16 carbon atoms, most preferably 12 to 15 carbon atoms. The alkoxylated alcohol is preferably an alkoxylated fatty alcohol, meaning that the alcohol portion has a carbon chain length of at least 8 carbon atoms.

The alkoxylated alcohol preferably has an average of 10 to 60 mol of ethylene oxide and 2 to 45 mol of propylene oxide per mol of alcohol; preferably 4 to 40 moles of propylene oxide per mole of alcohol.

The alkoxylated alcohol is preferably an ethylene oxide / propylene oxide adduct unit. More preferably, the alkoxylated alcohol is a fatty alcohol / ethylene oxide / propylene oxide adduct.

Preferably, the alkoxylated alcohol is a triblock copolymer of a fatty alcohol / ethylene oxide / propylene oxide or a fatty alcohol / propylene oxide / ethylene oxide of the general formula (I) or (II)

,

,

where A represents an alcohol moiety, R represents a hydrocarbon chain of 4 to 24 carbon atoms, B represents ethylene oxide units, and C represents propylene oxide units. The hydrophobic group R of a nonionic compound may be a straight or branched chain primary or secondary alcohol containing from 4 to 24 carbon atoms. Preferably, the number of carbon atoms in R is at least 4, preferably from 4 to 15. R is CH3- (CH2) x-. Preferably x is from 3 to 14; y and z are average values of the degree of ethoxylation and propoxylation, respectively, from 6 to 80 and from 2 to 60. Preferably, y is from 10 to 60 and z is from 2 to 45; preferably from 4 to 40.

Compounds represented by formulas (I) and (II) can be prepared by reacting an alcohol with ethylene oxide and propylene oxide. Ethoxylation and propoxylation of alcohols are methods known to those skilled in the art.

An alcohol alkoxylate of formula (I) or (II) can be obtained from an alcohol described as ROH, where R is CH ₃ - (CH ₂ ) _x —CH ₂ - and x is from 2 to 22. The alcohol may be butanol , hexanol, octanol or fatty alcohol. Alkoxylation is preferably achieved by ethoxylation and propoxylation.

The compound of formula (I) and (II) is preferably an alkoxylated fatty alcohol, more preferably an ethoxylated and propoxylated block copolymer, more preferably an ethoxylated and propoxylated fatty alcohol block copolymer with a carbon chain length of at least 4, preferably 4 to 15. Most preferably, a compound of the formula I represents the reaction product of a fatty alcohol with a carbon chain length of at least 4, preferably from 12 to 15, with 2-45 mol of propylene oxide and with 10-60 mol ethylene oxide.

They can be obtained by condensation of an alcohol containing from 4 to 16 carbon atoms in a straight or branched chain configuration, condensed with 10-60 mol of ethylene oxide and 2-45 mol of propylene oxide.

Most preferably, the alkoxylated alcohol compound is a triblock copolymer of structure ABC or ACB, where A is a fatty alcohol, B is polyethylene oxide and C is polypropylene oxide.

Preferably, the minimum number of average molecular weight of the alkoxylated alcohol, expressed in units of atomic weight, is at least 1000, more preferably at least 1500, most preferably at least 2500.

Suitable ethoxylated / propoxylated fatty alcohols for use in the invention may be commercially available under the Antarox trademark, available from Rhodia; Surfonic LF (Surfonic LF), which can be purchased from Huntsman; Tergitol XD Surfonic LF, Dow; Synperonic PE (Sinperonic PE), Surfonic LF, BASF; Atlas G5000, Surfonic LF, Uniqema; Dehypon available from Cognis; Tensiofix UNI01 (Tenziofiks UNI01) and Tensiofix AGCA22 (Tenziofiks AGCA22), available from Ajinomoto Omnichem.

More preferably, the alkoxylated alcohol is a polymer of α-alkyl-ω-hydroxypoly (hydroxypropylene) and poly (oxyethylene), where the alkyl chain contains at least four carbon and the minimum number of average molecular weight, expressed in units of atomic mass, is 1100.

Most preferably, the alkoxylated alcohol is α-alkyl (C ₁₂ -C ₁₅ ) -ω-hydroxypoly (hydroxypropylene) poly (oxyethylene) copolymers, where the poly (oxypropylene) content is 3-60 mol and the poly (oxyethylene) content is 5- 80 mol, where the ethoxylated / propoxylated (C ₁₂ -C ₁₅ ) alcohols obtained have a minimum molecular weight expressed in units of atomic mass of 1500. Such a product can be represented by the formula CH ₃ - (CH ₂ ) _10-13 -CH ₂ -O- (CH ₂ —CH ₂ —O) _3-60 - (CH (CH ₃ ) —CH ₂ —O) _5-80 —H. An example is represented by a compound with chemical number CAS 68551-13-3.

The composition of an embodiment of the invention is compatible with a wide range of pesticidal active ingredients. This makes it possible to reduce the number of compositions and types of raw materials that must remain in stock in order to produce a wide range of emulsifiable concentrates. It is cost effective.

The emulsifying system of the present invention is advantageous because only a few types of solvents miscible with water and surfactants need to be kept in stock at the industrial plant, which makes it possible to manufacture a wide range of commercial products using a limited number of raw materials.

The term "compatible", as used in this description of the invention, means that as a result of mixing them together there are no adverse effects. Incompatible mixtures can cause equipment damage, waste of time due to equipment failure, damage to target plants and chemical inefficiency. Incompatible mixtures may result from chemical or physical incompatibilities. Chemical incompatibility occurs when one or more chemicals change properties. Physical incompatibility causes lumps or gels to form. Chemicals do not disperse properly and precipitate from suspension. Incompatibility can also take the form of foams, lamination in the tank, discoloration and bubbles.

By the term “active ingredient”, as used herein, is meant an ingredient that is chemically active and / or biologically active in nature. The activity is directed against pests, especially plant pests. In this regard, the “active ingredient” may be a single ingredient or a combination of ingredients.

Active ingredients suitable for use in the present invention include insecticides such as abamectin, alpha-cypermethrin, cypermethrin, permethrin, deltamethrin, diflubenzuron, flufenoxuron, etofenprox, malathion, pymetrozine, pyriproxifen, azoxystrobinodorodinodilodorodilodilodilodilodlodlin dlorodilon dlorodinodilodorin dlorodinodlodorin , mancozeb, metconazole, spiroxamine, 2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ether (2,4-D EHE), chlorprofam (CIPC), celodime, metribuzin, prosulfocarb, pendimethalin, butoxyethyl butyl ether triclopyr and trinexapac-ethyl.

In a preferred embodiment, the composition further comprises a pesticidal active ingredient selected from the list: abamectin, chlorpyrifos-ethyl, cypermethrin, deltamethrin, diflubenzuron, phenoxycarb, indoxacarb, malathion, pymetrozine, pyriproxifen; azoxystrobin, captan, chlorothalonil, cyprodinil, dimetomorph, dodin, folpet, phosphetyl aluminum, iprodion, mancozeb, metconazole, spiroxamine, 2,4-dichlorophenoxyacetic acid (2,4-D acid), 2,4-dichlorophenoxyacetic acid, 2-ethyl ether (2,4-D EHE), chlorprofam (CIPC), celodim, glyphosate, 2-methyl-4-chlorophenoxyacetic acid (MCPA), metribuzin, prosulfocarb, pendimethalin, triclopyr, gibberellic acid, maleic acid gibrazide and trinexapac-ethyl.

In a preferred embodiment of the invention, the active ingredient is trinexapac-ethyl. Its effect is that the solution does not freeze at a temperature of 4 to 5 ° C.

In a preferred embodiment, a composition comprising trinexapac-ethyl as an active ingredient is as follows:

Trinexapac-ethyl: 250 g / l

Tensiofix UNI 1: 150 g / l

Tenziofiks D03: 200 g / l

Surfinol DF58: 2 g / l

Glycerol formal: 550 g / l

The surfactant Tenziofiks D03 acts as a biological activator. This surfactant is not necessary for the stability of the emulsion.

In a preferred embodiment of the composition, the selected pesticidal active ingredient is cypermethrin. By the term “cypermethrin”, as used herein, is meant alpha-cypermethrin, cypermethrin, beta-cypermethrin, zeta-cypermethrin; as well as mixtures thereof, derivatives or isomers.

Cypermethrin is an ISO-approved generic name for (RS) -α-cyano-3-phenoxybenzyl- (1RS, 3RS; 1RS, 3RS) -3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropane-carboxylate. Cypermethrin is a synthetic pyrethroid insecticide containing three chiral centers, forming a racemic mixture of eight isomers containing four diastereoisomeric pairs.

Alpha-cypermethrin is a racemate consisting essentially of two of the four cis isomers that make up cypermethrin, in particular the (S) -alpha-cyano-3-phenoxybenzyl- (1R, 3R) -3- (2,2- dichlorvinyl) -2,2-dimethylcyclopropanecarboxylate and (R) -alpha-cyano-3-phenoxybenzyl- (1S, 3S) -3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropanecarboxylate.

Beta-cypermethrin contains 4 of the 8 isomers that make up cypermethrin. Isomers in beta cypermethrin include 2 cis isomers (1S-cis-R and 1R-cis-S), which are isomers contained in alpha cypermethrin, and 2 trans isomers (1S-trans-R and 1R-trans -S). cis isomers have a greater insecticidal activity than trans isomers.

The term zeta-cypermethrin, as used herein, means (R, S) -α-cyano-3-phenoxybenzyl- (1RS) -cis-trans-3- (2,2-dichlorovinyl) -2,2- dimethylcyclopropanecarboxylate.

In a more preferred embodiment of the invention, the selected pesticidal active ingredient is cypermethrin.

In a more preferred embodiment of the invention, the selected pesticidal active ingredient is cypermethrin, the surfactant is an alkoxylated alcohol of formula (I) or (II), and the solvent is diethylene glycol monoethyl ether.

Examples of such alcohols, in particular, include primary alcohols, which may be linear or branched, especially mono-branched. The alkoxylated portions of such alcohols are mixed ethoxylates / propoxylates, which can be block or optionally mixed alkoxylates, usually containing from 6 to 80 mol of ethylene oxide and from 2 to 60 mol of propylene oxide, preferably when the polyalkoxylate chain terminates in propylene oxide units. Preferably, the polyoxyethylene / polyoxypropylene copolymers are block copolymers.

A preferred embodiment of the invention is a pesticidal composition wherein cypermethrin is present in an amount of 1% to 60%, the alkoxylated alcohol of formula (I) is present in an amount of 1% -20%, and diethylene glycol monoethyl ether is present in an amount of 25% -98%, where all percentages are% by weight, calculated based on the total weight of all components of the composition. In addition, the composition may contain from 0% to 10% water. Antifoam may be present in the composition in an amount of from 0% to 0.3%.

In a preferred embodiment, the composition comprises:

50% by weight of cypermethrin,

35% diethylene glycol monoethyl ether,

14.9% by weight of triblock copolymer of alcohol / ethylene oxide / propylene oxide and

0.1% antifoam.

In a preferred embodiment, the composition has a pH of 1 to 13, preferably the composition has a pH of 4 to 8, more preferably the pH of the composition is about 6.

The emulsifying system of the present invention is a system compatible with a wide range of active ingredients. This is preferable since only a limited amount of water-miscible solvents and surfactants can be stored at the facility, without limiting the range of commercial products that can be produced from a limited number of raw materials.

In another aspect of the invention, a method for producing an emulsifiable solution of pesticides and an emulsified pesticidal composition obtained from it is provided.

The method according to an embodiment of the invention for the manufacture of emulsifiable solutions of pesticides includes the steps of:

- selection of a water-miscible organic solvent from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone, or mixtures thereof,

- loading the solvent into a mixing vessel,

- adding to the selected solvent an alcohol alkoxylate of formula (I), where x is from 2 to 14, y is from 6 to 80 and z is from 2 to 60,

- mixing the solvent and alcohol alkoxylate to obtain a preemulsion for the pesticidal active ingredient.

By the term “preemulsion”, as used herein, is meant a composition suitable for the manufacture of an emulsifiable pesticide concentrate.

The choice of solvent is focused on the solubility of the active ingredient in the solvent.

The composition obtained as described above can serve as a solvent / surfactant pair for a wide range of pesticidal active ingredients. To obtain an emulsifiable solution of the pesticide, the pesticidal active ingredient miscible with the selected solvent / surfactant pair is added to the preemulsion. Miscibility can be checked using a standard solubility screening test known to one of skill in the art. The emulsifiable solution of pesticides obtained in this way can be stored until it is used to obtain an emulsified solution of pesticides.

Mixing can be carried out at room temperature or, preferably, at elevated temperature. In a preferred embodiment, the method includes the step of heating a solution containing the pesticidal active ingredient to a temperature of from 20 ° C to 60 ° C, preferably from 30 ° C to 60 ° C; more preferably up to about 40 ° C. Heating the mixture to a temperature of approximately 40 ° C facilitates the dissolution of pesticides.

In a preferred embodiment, the method includes the step of adding the emulsifiable composition to water, thereby producing an emulsified pesticidal composition, and applying the emulsified pesticidal composition to the crop to treat pests sensitive to the action of the selected active ingredient.

Active pesticidal ingredients may be used in the form of liquids or powders. After mixing with the emulsifying system of the invention, they are flowable emulsifiable compositions that are readily dispersible in water. The resulting emulsions are stable over time, usually of the order of at least 4 hours. The final product is not yet emulsified. When it is diluted with water, the emulsifiable composition will form an emulsion. The emulsion is stable for at least 4 hours.

The pesticidal composition of the invention is prepared by mixing a solvent miscible with the pesticidal composition in a concentration of from 10 g / L for a lower concentration (e.g., in the case of cypermethrin) to 800 g / L for a higher concentration (e.g., in the case of triclopyr butoxyethyl ether).

In a preferred embodiment, the composition of the invention is used to treat crops.

In a final aspect of the invention, there is provided a method of processing a crop, comprising the steps of:

- receiving a kit containing

(a) a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone or mixtures thereof,

(b) alkoxylated alcohol with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 2 to 60 mol per mole of alcohol; and

(c) a pesticidal active ingredient,

- mixing (a) with (b) and (c), thereby obtaining a solution for the manufacture of emulsifiable solutions of pesticides,

- adding water to this solution, emulsifying thereby the pesticidal active ingredient and obtaining an emulsified pesticidal composition containing the active ingredient with a predetermined dose level,

- applying an emulsified pesticidal composition to a crop affected by a disease that is sensitive to the action of the selected active ingredient and dose level.

In a preferred embodiment, the kit is accompanied by an information sheet with instructions for mixing the solvent, surfactant and pesticidal active ingredient to form an emulsifiable solution of the pesticide. The product information sheet may indicate specific concentrations of ingredients to be used. Specific examples of compositions may also be provided therein.

The present invention will now be described in more detail with reference to examples which are not limiting. It is intended that the present invention not be limited to any form of implementation described previously, and that some modifications may be added to the presented manufacturing example without reassessing the appended claims.

EXAMPLES

Example 1

In the experiment summarized in Table 1, emulsifiable solutions of pesticides were prepared based on a kit containing DMSO 40% + GBL 60%, Tenziofix UNI01, and selection from the group of active ingredients. First, the solvent DMSO40 / GBL60 was mixed with a non-ionic surfactant, in particular Tenziofix UNI01. The resulting mixture was divided into several samples. The selected active ingredient was added to the samples. The emulsifiable pesticide solution thus obtained was tested for emulsion stability. Cases were noted when a homogeneous mixture was obtained and when there were no noticeable amounts of precipitated pesticide.

Examples 2-4 provide further examples of emulsifiable compositions. To obtain an emulsion concentrate, water is added to the composition.

Example 2

Cypermethrin: 50%

Tensiofix UNI01: 14.9%

Surfinol DF58 (Defoamer): 0.1%

Carbitol: 35%

Example 3

Cypermethrin: 10%

Dovanol DPM: 82%

Tensiofix UNI01: 4%

Water: 4%

Example 4

Spiroxamine: 50%

Dovanol DPM: 35%

Tensiofix UNI01: 15%

Example 5

In the next experiment, pesticidal compositions containing various solvent / surfactant pairs were prepared. These include the solvent / surfactant pairs of the invention (Refs. 2-4) and others. The corresponding compositions are proposed in the columns "Active ingredient / surfactant / solvent / other." The amount of ingredients used is also indicated. After creating these compositions, the appearance of the final product was visually studied, which was then noted in the table. The result was reflected in the column “Appearance of the final product”. The composition was used to obtain emulsions as in the previous examples, 1% vol./about. After 1 hour, these 1% emulsions were again studied and the result was noted in the table in the column “Emulsion Stability”. The results were photographed.

Pluronic PE 10400 is an EO / PO block copolymer, in particular an ABA block copolymer containing 25 mol of ethylene oxide, 56 mol of propylene oxide and 25 mol of ethylene oxide, which provides the chemical structure of EO ₂₅ PO ₅₆ EO ₂₅ .

Sinperonic PE / P105 is an EO / PO block copolymer, in particular an ABA block copolymer containing 37 mol of ethylene oxide (EO), 56 mol of propylene oxide (PO) and 37 mol of ethylene oxide (EO), providing the chemical structure of EO ₃₇ PO ₅₆ EO ₃₇ .

Genapol EP 0244 is an alcohol alkoxylate, in particular C10 / C12 alcohol with 4 EO followed by 4 PO.

The tensiofix UNI01 is an alkoxylate with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 4 to 60 mol per mole of alcohol.

As can be seen from the results presented in Tables 2-4, the solvent / surfactant formulations of the invention gave homogeneous and stable emulsions. No precipitate was observed after 1 hour in water according to CIPAC D (International Joint Analytical Council for Pesticides) at 20 ° C.

For other solvent / surfactant pairs, where the solvent remained the same and the surfactant was similar, they could not obtain a homogeneous emulsion without the formation of a precipitate or crystallization.

Claims (62)

1. A kit for the manufacture of an emulsifiable solution of a pesticide, containing: (a) a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone or mixtures thereof, (b) an alkoxylated alcohol having an alkyl chain of 4 to 24 carbon atoms in length, with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 2 to 60 mol per mole of alcohol; and (c) a pesticidal active ingredient, where alkoxysilane alcohol has the formula (I) or (II)

x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60; provided that there is no aromatic or isoparaffin solvent. 2. The kit of claim 1, wherein the solvent is dipropylene glycol methyl ether, diethylene glycol monoethyl ether or dipropylene glycol monoethyl ether. 3. The set according to claim 1 or 2, where x is from 2 to 14, y is from 10 to 60 and z is from 2 to 45. 4. The kit according to claim 1 or 2, where the pesticidal active ingredient is selected from the list: abamectin, alpha-cypermethrin, cypermethrin, permethrin, deltamethrin, diflubenzuron, flufenoxuron, etofenprox, malathion, pymetrozine, pyriproxifen, azoxystrobilin, cyclotrin, cycl dodin, iprodion, mancozeb, metconazole, spiroxamine, 2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ether (2,4-D EHE), chlorprofam (CIPC), celodim, metribuzin, prosulfocarb, pendimethalin, butoxyethyl tripleclopyr ether, and their mixture. 5. The kit according to claim 1 or 2, where the selected pesticidal active ingredient is cypermethrin, isomer of cypermethrin, or mixtures thereof. 6. The kit of claim 5, wherein the pesticidal active ingredient is cypermethrin. 7. The kit according to claim 1 or 2, where the selected pesticidal active ingredient is trinexapac-ethyl. 8. A composition for the manufacture of emulsifiable solutions of pesticides obtained from the kit according to claim 1, containing: (a) a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone, or mixtures thereof; and (b) an alkoxylated alcohol having an alkyl chain of 4 to 24 carbon atoms in length, with ethylene oxide in an amount of on average 6 to 80 mol and with propylene oxide in an amount of on average 2 to 60 mol per mole of alcohol, where alkoxysilane alcohol has the formula (I) or (II)

x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60; provided that there is no aromatic or isoparaffin solvent. 9. The composition of claim 8, wherein the solvent is dipropylene glycol methyl ether, diethylene glycol monoethyl ether or dipropylene glycol monoethyl ether. 10. The composition according to claim 8 or 9, where x is from 2 to 14, y is from 10 to 60 and z is from 2 to 45. 11. The composition according to p. 8 or 9, where the pesticidal active ingredient is selected from the list: abamectin, alpha-cypermethrin, cypermethrin, permethrin, deltamethrin, diflubenzuron, flufenoxuron, etofenprox, malathion, pymethrosine, pyriproxifen, azroxystorilon cyclin, x dodin, iprodion, mancozeb, metconazole, spiroxamine, 2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ether (2,4-D EHE), chlorprofam (CIPC), celodim, metribuzin, prosulfocarb, pendimethalin, butoxyethyl tripleclopyr ether, and their mixture. 12. The composition according to p. 8 or 9, where the selected pesticidal active ingredient is cypermethrin, isomer of cypermethrin or mixtures thereof. 13. The composition of claim 12, wherein the pesticidal active ingredient is cypermethrin. 14. The composition of claim 8 or 9, wherein the selected pesticidal active ingredient is trinexapac-ethyl. 15. The composition according to p. 13, containing: 25-98% diethylene glycol monoethyl ether, 1-20% alkoxylated alcohol as defined in paragraph 8, 1-60% cypermethrin, 0-10% water and 0-0.3% antifoam. 16. A composition for the manufacture of emulsifiable solutions of pesticides, containing: 250 g / l trinexapac-ethyl 150 g / l of alkoxylated alcohol having an alkyl chain of 4 to 24 carbon atoms in length, with an average of 6 to 80 mol ethylene oxide and an average of 2 to 60 mol of propylene oxide per mole of alcohol, where alkoxysilane alcohol has the formula (I) or (II)

x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60; 550 g / l glycerolformal. 17. A method of manufacturing emulsifiable solutions of pesticides, comprising the steps of: - obtaining a solution containing a water-miscible organic solvent selected from the list: propylene glycol ether, glycerol formal, dimethyl sulfoxide and gamma-butyrolactone or a mixture thereof; and an alkoxylated alcohol having an alkyl chain of 4 to 24 carbon atoms in length, with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 2 to 60 mol per mole of alcohol, and - adding to this solution a pesticidal active ingredient miscible with the selected solvent, where alkoxysilane alcohol has the formula (I) or (II)

x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60; provided that there is no aromatic or isoparaffin solvent. 18. The method according to p. 17, comprising the stage of: - heating the solution containing the pesticidal active ingredient to a temperature of from 20 ° C to 60 ° C. 19. A method of processing a crop, comprising the steps of: - receiving a kit containing: (a) a water-miscible organic solvent selected from the list: glycol ether, glycerol formal, dimethyl sulfoxide, gamma-butyrolactone or mixtures thereof, (b) an alkoxylated alcohol having an alkyl chain of 4 to 24 carbon atoms in length, with ethylene oxide in an average amount of 6 to 80 mol and with propylene oxide in an average amount of 2 to 60 mol per mole of alcohol; and (c) a pesticidal active ingredient, where alkoxysilane alcohol has the formula (I) or (II)

x is from 2 to 22, y is from 6 to 80 and z is from 2 to 60; provided that there is no aromatic or isoparaffin solvent, - mixing (a) with (b) and (c), thereby obtaining a solution for the manufacture of emulsifiable solutions of pesticides, - adding water to this solution, emulsifying thereby the pesticidal active ingredient and obtaining an emulsified pesticidal composition containing the active ingredient with a predetermined dose level, - applying an emulsified pesticidal composition to a crop affected by a disease that is sensitive to the action of the selected active ingredient and dose level. 20. The method according to any one of paragraphs. 17-19, where the active ingredient is cypermethrin or trinexapac-ethyl.